CN104637551B - Ti3SiC2Base ceramic material is used as the resistance to application for melting fluoride salt corrosion material - Google Patents
Ti3SiC2Base ceramic material is used as the resistance to application for melting fluoride salt corrosion material Download PDFInfo
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Abstract
The present invention proposes Ti3SiC2Base ceramic material is used as the resistance to application for melting fluoride salt corrosion material.The present inventor has found Ti by many experiments3SiC2Corrosion rate of the base ceramic material in melting villiaumite is extremely low, and its resistance to melting fluoride salt corrosion performance inert metal nickel best with resistance to melting fluoride salt corrosion ability at present and nickel base superalloy are in the same order of magnitude, therefore Ti3SiC2Base ceramic material is used as fusedsalt reactor structural material, such as cladding materials, container material, pipeline material, and the spentnuclear fuel dry method post processing function electrode material by electrolyte of villiaumite is applied, it also can be coated on alloy surface as resistance to melting fluoride salt corrosion film or coating material and apply.
Description
Technical field
The present invention relates to Ti3SiC2Base ceramic material technical field, more particularly to the ceramic material are rotten as resistance to melting villiaumite
The application of corrosion material.
Background technology
China is an energy micro state, and petroleum resources are quite poor, and in particular with economic fast development, country is to energy
The demand in source is increasingly increased, therefore energy problem is related to stabilization and the development of country.At present, thermoelectricity is accounted in State Grid's production
About 80%, water power accounts for about 16%, and remaining is wind-power electricity generation, nuclear power etc..Wherein, nuclear energy there is the high and low carbon emission of energy density, it is potential
The advantage such as sustainable developability, in the case of Global climate change, energy-saving and emission-reduction, low-carbon economy are just promoting nuclear energy in the whole world
Revive.But, accounting of the nuclear power in China's energy resource structure is only 1.12%, and in the flourishing France of nuclear power, nuclear power is in electric power knot
Proportion reaches 80% in structure, therefore greatly develops emphasis of the nuclear energy as China's energy Long-and Medium-term Development planning.
However, Nuclear Power Development is also faced with problems.One of problem is that we lack uranium used in traditional nuclear power
Fuel.But, China possesses abundant thorium raw material, and thorium is converted into the technical method of uranium by research, using advanced MSR skill
Art develops safer, more cleaning, the final also more economical forth generation fission reactor nuclear power system based on thorium ---
Thorium base MSR nuclear power system（TMSR）Safety, the fuel problem of fission-type reactor can preferably be solved.
Melting villiaumite has low melting point, higher boiling, low-steam pressure, high specific heat capacity and thermal conductivity, high chemical stability, low
The advantages of density is high is depressed, is expected to as the extensive use in MSR technology of fusedsalt reactor fuel salt.In addition, melting villiaumite
Also it is widely applied in terms of Main Coolant, heat transferring medium, spentnuclear fuel dry method post processing electrolyte.
But, operating temperature height, the corrosivity for melting villiaumite are strong, it is desirable to contain the container of the melting villiaumite or molten in this
The structural material melted in villiaumite environment has the excellent fluoride salt corrosion of resistance to melting.For example, what is used in fusedsalt reactor is molten
Melting villiaumite needs for a long time in high temperature（I.e. villiaumite fusing point is with up to 1000 DEG C of temperature range）Lower operation, it is necessary to core involucrum material
The structural materials such as the pipeline expect, contained the container of fuel fused salt and contain heat exchange salt have excellent high temperature resistant and the villiaumite of resistance to melting
Corrosivity；In the dry method post processing of reactor spentnuclear fuel, fluoride is typically in 550-650 DEG C of temperature section work, it is necessary to enter
The container and electrode material of row lock out operation have the dual property of high temperature resistant chemical attack and electrochemical corrosion.
At present, show about the fluoride salt corrosion of the resistance to melting performance study of structural material, most of traditional high temperature alloy materials
Expect that oxidation and heat erosion in corrosion and air under melting villiaumite environment have essential distinction.Different from traditional air and
Oxidation in the aqueous solution, in melting villiaumite environment, the oxide-film majority of material surface protectiveness can occur dissolving thus not have
Protective.
For example, NASA（NASA）Researcher find that common higher temperature alloy material corrodes tight in melting villiaumite
Weight, with Ni, Co, Fe, Cr, Al, this order increases the corrosion tendency of each component successively, for multi-component alloys, active metal meeting
Generation selective oxidation and dissolving, cause whole alloy material to fail；They are it has also been found that the refractory metal material such as Nb, Mo and W simultaneously
Material, the extent of corrosion of Ni-Mo base Hastelloy B alloy materials is relatively low, but piece of refractory metal material inoxidizability is very poor,
Serious embrittlement after Hastelloy B alloy materials are on active service at 650-815 DEG C, and oxidation resistance is poor, thus it is used as structure group
Part, which is chronically exposed to problem in air, to be still present.
U.S.'s Oak Ridge National Laboratory（ORNL）Research show Inconel（（15%Cr,7%Fe,78%Ni）Alloy exists
With NaF-ZrF4-UF4（53.09-40.73-6.18mol%）For the fused salt reaction experiment heap of fuel salt（MSRE）It is middle to be used as container
Material corrosion situation is serious, and main corrosion mechanism is the selective dissolution of Cr elements.They then specially devise modified nickel
Based alloy Hastelloy-N（17%Mo7%Cr, 5%Fe, remaining be Ni）, but Hastelloy-N lacks other Ni-based and iron nickel
The elevated temperature strength that based alloy has, thus the reliability of long service remains unsolved.
The research of Wisconsin-Madison universities shows, common high temperature alloy Hastelloy-X, Haynes-
230th, Inconel-617 suffers from serious corrosion in high temperature FLINAK fused salt environment, and Ni-201（Ni contents are more than
90%）Good corrosion resistance is shown, but the pure nickel material of element state lacks due elevated temperature strength as construction package,
Pyrolytic carbon（PyC）/ SiC coatings can improve the corrosion resistance of C/Si/SiC composites, and Ni, Mo coating also can be in certain journeys
On degree improve high-temperature alloy material corrosion resistance, but there are problems that high temperature peel off and.
The content of the invention
The inventors discovered that, Ti3SiC2Ceramic material and Ti3SiC2Composite ceramic material, i.e. Ti3SiC2Base ceramic material has
There is resistance to melting fluoride salt corrosion characteristic.
Ti3SiC2Base ceramic material is the new high-temperature structural material of a class, and existing result of study shows, this kind of material
With unique nano-lamellar structure, both there is low-density, high resiliency rigidity, high temperature resistant and oxidative resistance as ceramics, again
As metal anti-thermal shock, easy processing, with high damage tolerance, and higher thermal conductivity and electrical conductivity, therefore in recent years
As a class high temperature structural material by extensive concern.But, up to now, on Ti3SiC2The resistance to melting of base ceramic material
Villiaumite characteristic has not been reported.
The present inventor is to Ti3SiC2Corrosion behavior of the base ceramic material in fused salt has carried out system research, finds
Ti3SiC2Corrosion rate of the base ceramic material in melting villiaumite is extremely low, the best inertia with resistance to melting fluoride salt corrosion ability at present
Metallic nickel and nickel base superalloy are in the same order of magnitude, therefore, it is possible to be applied as resistance to melting fluoride salt corrosion material.
Meanwhile, Ti3SiC2Base ceramic material, which has, is used as the due good mechanical behavior under high temperature of structural material and anti-oxidant
Property, also with as functional electrode material due excellent high heat conductance, electrical conductivity, heat endurance and chemical stability,
Therefore it is a kind of good fluoride salt corrosion of the resistance to melting material of combination property, can be such as wrapped as fusedsalt reactor structural material
Shell material, container material, pipeline material, and it is used as the spentnuclear fuel dry method post processing functional electrode material using villiaumite as electrolyte
Expect and apply, also can be coated on alloy surface as resistance to melting fluoride salt corrosion film or coating material and apply.
Heretofore described Ti3SiC2Base ceramic material includes Ti3SiC2Ceramic material, i.e. its chemical formula are
Ti3SiC2, also including Ti3SiC2The composite ceramic material constituted with compound phase.The present inventor by experiment find, when with
Ti3SiC2Ceramic material is as matrix, with the compound phase with decay resistance, such as SiC, ZrB2、 TiC、Ni、Mo、Nb、W、
Prepared by Cu, C, Ti, Hf, Ta etc. carry out compound composite, with preferably resistance to melting fluoride salt corrosion ability, can enter one
Corrosion rate of the step reduction material in melting villiaumite environment.Preferably, the content of compound phase in the base is 0.01-
90wt%.The incorporation way of compound phase includes high-temp in-situ and generates and directly added in raw material powder.Directly added in raw material powder
Compound phase refers to by Ti3SiC2The powder of powder and compound phase by certain stoichiometric proportion weigh mixing after obtained through sintering.
High-temp in-situ generation refers to respectively by Ti3SiC2Stoichiometry and the stoichiometric proportion of compound phase weigh each element powder, so
Sintered by conventional electric resistance, microwave sintering, hot pressed sintering or plasma discharging Fast Sintering technology it is anti-by high-temp in-situ
Compound phase should be introduced, corresponding composite ceramic material is made.
Heretofore described villiaumite is FLINAK, and the fluorine-containing salt-mixture such as FLIBE, wherein FLINAK is anti-as fused salt
Heap Main Coolant is answered to be expected to be used in forth generation MSR.
The test of resistance to melting fluoride salt corrosion performance of the present invention is carried out in melting villiaumite.Method of testing is：Will
Ti3SiC2It is put into after the polishing of base ceramic material sample surfaces in the graphite crucible in glove box, under inert atmosphere protection, by block
Shape villiaumite is put into graphite crucible, and then graphite crucible is put into container and sealed, afterwards takes out container simultaneously from glove box
Temperature is heated between villiaumite fusing point（When villiaumite is composition, the fusing point is the eutectic point of composition）With 1000 DEG C it
Between, make Ti3SiC2Base ceramic material, which is immersed in the villiaumite of the melting, to be corroded 1-30 days；After corrosion experiment terminates, by Ti3SiC2
Base ceramic material sample takes out cleaning, dried.The size and weight of sample are measured, obtains testing the size and weight of front and rear sample
Change；The microstructure change of sample surfaces and section is observed using SEM, using EDS observing samples surface and the composition of section
Change.
Ti of the present invention3SiC2When base ceramic material is applied as resistance to melting fluoride salt corrosion material, body can be used as
Material is directly used in fusedsalt reactor structural material, cladding materials, container material, pipeline material, and using villiaumite as electrolysis
The spentnuclear fuel dry method post processing fields such as functional electrode material material of matter, also can be coated on common alloys as film or coating
Surface and be used for above field.The Ti3SiC2Base bulk ceramic material is typically burnt using conventional electric resistance, hot pressed sintering, microwave
Knot or plasma discharging Fast Sintering technology are prepared.The preparation method of film or coating material includes but is not limited to physics gas
Phase sedimentation, is such as sputtered（High-power impulse magnetron sputtering, d.c. sputtering, reactive sputtering）, cathodic arc deposition, pulse laser sink
Product；Chemical vapour deposition technique；Solid reaction process；Hot spray process.
In order to further improve the Ti3SiC2The fluoride salt corrosion of the resistance to melting performance of ceramic material, it is preferred to use consistency is high
Ti3SiC2Base Bulk ceramic.It is experimentally confirmed that when using plasma discharging Fast Sintering（SPS）During technology, prepare
Ti3SiC2Base Bulk ceramic has higher consistency and smaller crystallite dimension.The preparation method is specially：By Ti3SiC2's
Stoichiometric proportion is weighed each element powder, it is well mixed after fire and form through SPS equipment.
Brief description of the drawings
Fig. 1 is the preceding Ti of FLINAK fused salt corrosions experiment in the embodiment of the present invention 13SiC2The XRD spectrums of sample；
Fig. 2 is Ti after the experiment of FLINAK fused salt corrosions in the embodiment of the present invention 13SiC2The XRD spectrums of sample；
Fig. 3 is Ti after the experiment of FLINAK fused salt corrosions in the embodiment of the present invention 13SiC2The section SEM figures and EDS knots of sample
Really；
Fig. 4 is that alumina-base material passes through and Ti in embodiment 13SiC2It is disconnected after the experiment of sample identical FLINAK fused salt corrosions
Face SEM schemes and EDS results；
Fig. 5 is the preceding Ti of FLINAK fused salt corrosions experiment in the embodiment of the present invention 23SiC2The section of-SiC ceramic matrix composite material sample
SEM schemes；
Fig. 6 is Ti after the experiment of FLINAK fused salt corrosions in the embodiment of the present invention 23SiC2The XRD of-SiC ceramic matrix composite material sample
Spectrum；
Fig. 7（a）It is unit area weight-loss ratio block diagram of the high temperature alloy reported in document 1 in FLNAK fused salts；
Fig. 7（b）It is Ti in embodiment 1, embodiment 33SiC2And unit area of the alumina-base material in FLNAK fused salts is weightless
Rate block diagram.
Embodiment
The embodiment of the present invention is described further with embodiment below in conjunction with accompanying drawing, it should be pointed out that
Embodiment described below is intended to be easy to the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1：
In the present embodiment, to single-phase Ti3SiC2Block body ceramic material carries out resistance to melting fluoride salt corrosion experiment.
The single-phase Ti3SiC2Block is prepared using the method for powder sintering, is specially：Weigh appropriate business Ti3SiC2Powder
Body, by the Ti3SiC2Powder, which is fitted into graphite jig, first unidirectionally pressurizes into biscuit, is then placed in discharge plasma sintering（SPS）
In stove, 1200 DEG C are warming up under vacuum conditions, and applies 40MPa pressure, and soaking time is 5min.
To Ti obtained above3SiC2The thing of block materials mutually measures analysis, and its XRD is composed as shown in figure 1, can see
Go out that the block materials purity is very high, dephasign content is very low.
The Ti3SiC2The fluoride salt corrosion of the resistance to melting experimental method of block materials is：By the single-phase Ti3SiC2Block materials are used
Linear cutter equipment is processed into the cuboid sample that size is 30 × 10 × 2mm, and sample is fixed into graphite with C276 bolts
On rod.Then in glove box under Ar gas atmosphere protections, the graphite rod for fixing sample is put into graphite crucible, then to stone
About 500g bulk FLINAK fused salts are filled in black crucible, the villiaumite is by 46.5mol%LiF, 11.5mol%NaF and 42mol%KF group
Into（The eutectic point of the FLINAK salt is 452 DEG C）.The graphite crucible covered is loaded in 316 stainless cylinder of steel and welded seal.
The stainless cylinder of steel of good seal is put into resistance furnace, 700 DEG C are warming up to, now FLINAK salt is in molten state, sample is immersed in this
Melt in villiaumite and corrode 8 days（192h）.The villiaumite that corrosion remains sample surfaces after terminating is cleaned, then by batten in vacuum drying
Toasted in case.
Interpretation of result：The size and again of sample before and after slide measure and balance measurement melting fluoride salt corrosion experiment is respectively adopted
Amount；Influence of the FLINAK fused salts to sample surfaces and section is observed using SEM；Using EDS observing samples surface and section into
Divide change；As a result it is as follows.
（1）Above-mentioned single-phase Ti3SiC2Block materials sample is through the size and weight measurement before and after FLINAK fused salt corrosions
Show, after 700 DEG C of FLINAK fused salt corrosions 8 days, Ti3SiC2The size of sample remains unchanged substantially, and per unit is weightless
Measure as 4.8mg/cm2（Such as Fig. 7（b）It is shown）, illustrate the Ti3SiC2Sample has the excellent fluoride salt corrosion of resistance to melting performance.
（2）Through the single-phase Ti after above-mentioned resistance to melting fluoride salt corrosion experiment3SiC2The XRD of block materials sample is composed such as Fig. 2 institutes
Show, it can be seen that the sample top layer Si elements are lost, and TiC phases are decomposed under FLINAK fused salt etches.
After above-mentioned resistance to melting fluoride salt corrosion experiment, Ti3SiC2Block materials sample macroscopically keeps complete, and surface is still
With metallic luster, its section SEM figures and EDS results are as shown in Figure 3.From figure 3, it can be seen that Ti3SiC2Sample is in FLINAK
Corrosion in fused salt is mainly the selective dissolution of Si elements, but only can't detect Si elements, explanation in the μ m thick of top layer 80
Corrosion rate is very low.Further, since sample not 100% densification, thus still there is very small amount fused salt to penetrate into material internal, because
And EDS detects the elements such as a small amount of F, Na, K.
（3）For the sake of contrasting, the same fluoride salt corrosion of resistance to melting is carried out using alumina-base material sample and tested.Fig. 4 is this
It is section SEM figure and EDS result figure of the alumina-base material sample after melting fluoride salt corrosion experiment.It can be seen that section Al elements are several
All lose, fused salt is penetrated into inside batten.It is computed, alumina-base material sample unit area weight-loss ratio is 109mg/cm2（Such as
Fig. 7（b）It is shown）, it is Ti3SiC2More than 20 times of material.
（4）In order to further illustrate the single-phase Ti3SiC2The fluoride salt corrosion of the resistance to melting performance of material sample, by above-mentioned warp
Ti after FLINAK fused salt corrosions3SiC2Unit area weight-loss ratio and winconsin university Olson of sample et al. are in document 1：
Luke C.Olson,James W.Ambrosek,Kumar Sridharan,Mark H. Anderson,and Todd
R.Allen,“Materials corrosion in molten LiF–NaF–KF salt,”J. Fluorine Chem.130
Corrosion weight loss data of the Ni based high-temperature alloys material reported in (2009) 67-73. in the FLINAK fused salts（Such as Fig. 7（a））
Contrasted.As can be seen that the Ti in the present embodiment3SiC2The unit area weight-loss ratio of sample between Hastelloy-N and
Between Hastelloy-X, and Hastelloy-N is U.S.'s Oak Ridge National Laboratory（ORNL）On the basis of Hastelloy-X,
For fused salt reaction experiment heap（MSRE）Specially design improved structural material.This also illustrates the Ti3SiC2Material has excellent resistance to
Melt fluoride salt corrosion performance.
Therefore, as materials such as Ni based alloys, the Ti3SiC2Material can be answered as the resistance to melting fluoride salt corrosion material of one kind
With.In addition, compared with the materials such as Ni based alloys, the Ti3SiC2The unique nano-lamellar structure of material causes it to be provided simultaneously with metal
And with than Ni base alloy material more preferably mechanical behavior under high temperature and inoxidizability, therefore it is one with the premium properties of ceramics
The more excellent fluoride salt corrosion of the resistance to melting material of kind of combination property, can as fusedsalt reactor structural material, such as cladding materials,
Container material, pipeline material, and spentnuclear fuel dry method post processing function electrode material by electrolyte of villiaumite etc. are applied.
Embodiment 2：
In the present embodiment, to Ti3SiC2- 10wt%SiC composite block materials carry out resistance to melting fluoride salt corrosion experiment.
The composite is Ti3SiC2- 10wt%SiC, subsequent corrosion test is carried out in 700 DEG C of FLINAK fused salts, rotten
The erosion time is 8 days（192h）.Detailed process is as follows：
The Ti3SiC2- 10wt%SiC composite block materials are with Ti3SiC2Ceramic material is as matrix, using SiC as compound
Phase, the compound phase accounts for the 10wt% of matrix content.
The composite block material is prepared using the method for powder sintering, is specially：Weigh appropriate business Ti3SiC2With SiC powder
Body, ball milling is mixed, and is put into after drying in graphite jig, first unidirectionally pressurizes into biscuit, is then placed in discharge plasma sintering
（SPS）In stove, 1350 DEG C are warming up under Ar atmosphere protections, and applies 35MPa pressure, soaking time is 5min.
Ti obtained above3SiC2The section SEM figures of -10wt%SiC composite block materials are as shown in Figure 5.Can from Fig. 6
Go out, sinter obtained composite very fine and close.EDS results show that the nanoscale spherical particle in Fig. 6 is SiC phases, micron order
Stratiform crystalline substance is Ti3SiC2Phase, SiC is nanocrystalline to be dispersed in Ti3SiC2In matrix.
The Ti3SiC2In the fluoride salt corrosion of the resistance to melting experimental method and above-described embodiment 1 of -10wt%SiC composite block materials
Experimental method it is identical.
Interpretation of result：Slide measure and assay balance is respectively adopted to measure sample size and weight；Observed using SEM
Influence of the FLINAK fused salts to sample surfaces and section；It is as a result as follows using EDS observing samples surface and section.
（1）Above-mentioned Ti3SiC2- 10wt%SiC composite samples are surveyed through the size before and after FLINAK fused salt corrosions and weight
Amount result shows, after 700 DEG C of FLINAK fused salt corrosions 8 days, Ti3SiC2The size of sample remains unchanged substantially, mean unit face
Product weight loss is 4mg/cm2, illustrate the Ti3SiC2- 10wt%SiC samples have the excellent fluoride salt corrosion of resistance to melting performance.
（2）Through the Ti after above-mentioned resistance to melting fluoride salt corrosion experiment3SiC2The XRD spectrums of -10wt%SiC samples are as shown in Figure 7.With
Single-phase Ti in Fig. 23SiC2Block materials sample is compared, composite surface Ti after melting fluoride salt corrosion3SiC2Phase is only sent out
First portion is decomposed, and detects some TiC phases, the loss of Si elements substantially weakens, and single-phase Ti3SiC2Block materials surface Si members
Plain to lose completely, the selective dissolution of Si elements can be significantly reduced by showing the addition of SiC phases, so as to reduce melting fluoride salt corrosion speed
Rate, keeps matrix Ti3SiC2The stability of microstructure.Therefore, with single-phase block Ti3SiC2Material is compared, compound phase Ti3SiC2
The fluoride salt corrosion of resistance to melting of material is significantly improved.
Therefore, as the Ti in embodiment 13SiC2Monophase materialses, the Ti3SiC2Based composites also can be as a kind of resistance to
Melt fluoride salt corrosion material and apply, and the more single-phase Ti of its resistance to melting fluoride salt corrosion3SiC2Material is significantly improved, therefore is
A kind of more excellent fluoride salt corrosion of the resistance to melting material of combination property, can as fusedsalt reactor structural material, cladding materials,
Container material, pipeline material and spentnuclear fuel dry method post processing function electrode material by electrolyte of villiaumite etc. are applied.
Embodiment 3：
In the present embodiment, to single-phase Ti3SiC2Block body ceramic material carries out resistance to melting fluoride salt corrosion experiment.
The single-phase Ti3SiC2The preparation method of block body ceramic material is identical with the preparation method of embodiment 1.
The Ti3SiC2The fluoride salt corrosion of the resistance to melting experimental method of block materials is substantially same as Example 1, except that
850 DEG C are warming up to, etching time is 6 days（144h）.
Interpretation of result：The size of slide measure and the front and rear sample of assay balance measurement melting fluoride salt corrosion experiment is respectively adopted
And weight；Influence of the FLINAK fused salts to sample surfaces and section is observed using SEM；Using EDS observing samples surface and section
Composition transfer.
（1）Above-mentioned single-phase Ti3SiC2Block materials sample is through the size and weight measurement before and after FLINAK fused salt corrosions
Show, after 850 DEG C of FLINAK fused salt corrosions 6 days, Ti3SiC2The size of sample remains unchanged substantially, and thickness change is zero, puts down
Equal unit area weight loss is 9mg/cm2（Such as Fig. 7（b）It is shown）, corrosion experiment temperature is improved to after 850 DEG C, and weight-loss ratio is not
Dramatically increase, illustrate Ti3SiC2Sample has the excellent fluoride salt corrosion of a resistance to melting performance, and aluminium base under same experimental conditions
The unit area weight loss for expecting sample is 363mg/cm2（Such as Fig. 7（b）It is shown）, about Ti3SiC240 times of sample.
（2）Section SEM and EDS analysis result are similar to embodiment 1, and only Si elements in top layer are lost, and decomposed is into TiC
Phase.
Therefore, the Ti3SiC2Material has the excellent fluoride salt corrosion of resistance to melting ability, can be rotten as a kind of resistance to melting villiaumite
Corrosion material and apply.
Embodiment 4~12：
In embodiment 4~12, to single-phase Ti3SiC2Block body ceramic material carries out resistance to melting fluoride salt corrosion experiment.
The single-phase Ti3SiC2The preparation method of block body ceramic material is identical with the preparation method of embodiment 1.
The Ti3SiC2The fluoride salt corrosion of the resistance to melting experimental method of block materials is substantially same as Example 1, except that
Control to corrosion parameter is as shown in table 1 below.
Ti in the embodiment 4~12 of table 13SiC2The corrosion parameter of material is set
| Embodiment | The thing phase composition of batten before corrosion | Corrosion experiment temperature（℃） | Etching time（h） |
| 4 | Ti3SiC2 | 850 | 192 |
| 5 | Ti3SiC2 | 900 | 192 |
| 6 | Ti3SiC2 | 700 | 384 |
| 7 | Ti3SiC2 | 850 | 384 |
| 8 | Ti3SiC2 | 900 | 384 |
| 9 | Ti3SiC2 | 460 | 144 |
| 10 | Ti3SiC2 | 500 | 200 |
| 11 | Ti3SiC2 | 600 | 500 |
| 12 | Ti3SiC2 | 1000 | 72 |
Above-mentioned single-phase Ti3SiC2Block materials sample is through the size before and after FLINAK fused salt corrosions and weight measurement table
It is bright, after FLINAK fused salt corrosions, Ti3SiC2The size of sample remains unchanged substantially, thickness change very little, per unit
Weightless also very little, illustrates the Ti3SiC2Sample has the excellent fluoride salt corrosion of resistance to melting performance, can be used as a kind of resistance to melting
Fluoride salt corrosion material and apply.
Embodiment 13~24：
In embodiment 13~24, to Ti3SiC2Composite block material carries out resistance to melting fluoride salt corrosion experiment.
The Ti3SiC2The preparation method of composite block ceramic material is identical with the preparation method of embodiment 2.
The Ti3SiC2The fluoride salt corrosion of the resistance to melting experimental method of composite block ceramic material is substantially same as Example 2, institute
The difference is that SiC or C mass fraction and corrosion experiment parameter setting, as shown in table 2 below.
Ti in the embodiment 13~24 of table 23SiC2Based composite ceramic material preparation condition and corrosion parameter are set
Above-mentioned Ti3SiC2Based composite ceramic material sample is through the size and weight measurement before and after FLINAK fused salt corrosions
Show, after FLINAK fused salt corrosions, the size and weight of sample remain unchanged substantially, per unit weight loss is also very
It is small, illustrate the Ti3SiC2Based composites sample has the excellent fluoride salt corrosion of resistance to melting performance, can be used as a kind of resistance to melting
Fluoride salt corrosion material and apply.
Technical scheme and beneficial effect are described in detail embodiment described above, it should be understood that
The specific embodiment of the present invention is the foregoing is only, is not intended to limit the invention, it is all to be done in the spirit of the present invention
Any modification and improvement etc., should be included in the scope of the protection.Embodiment described above is to the present invention's
Technical scheme and products characteristics are described in detail, it should be understood that the foregoing is only the specific embodiment of the present invention, and
The limitation present invention, all any modification and improvement done in the spirit of the present invention etc. are not used in, this hair is should be included in
Within bright protection domain.
Claims (8)
1.Ti3SiC2Base ceramic material melts villiaumite as resistance to FLINAK or resistance to FLIBE melts the application of villiaumite material；It is described
Villiaumite be the fluorine-containing salt-mixtures of FLINAK or FLIBE；
It is resistance to melting fluoride salt corrosion performance method of testing be：By Ti3SiC2Glove box is put into after the polishing of base ceramic material sample surfaces
In interior graphite crucible, under inert atmosphere protection, block villiaumite is put into graphite crucible, graphite crucible is then put into appearance
Sealed in device, container taken out from glove box afterwards and temperature is heated between the eutectic point of villiaumite and 1000 DEG C,
Make Ti3SiC2Base ceramic material, which is immersed in the villiaumite of the melting, to be corroded 1-30 days.
2. Ti as claimed in claim 13SiC2Base ceramic material melts villiaumite as resistance to FLINAK or resistance to FLIBE melts fluorine
The application of salt material, it is characterized in that：Described Ti3SiC2The chemical formula of base ceramic material is Ti3SiC2。
3. Ti as claimed in claim 13SiC2Base ceramic material melts villiaumite as resistance to FLINAK or resistance to FLIBE melts fluorine
The application of salt material, it is characterized in that：Described Ti3SiC2Base ceramic material is single-phase Ti3SiC2Ceramic material, or with Ti3SiC2
For matrix, it is combined and is made with the compound phase with corrosion resistance.
4. Ti as claimed in claim 33SiC2Base ceramic material melts villiaumite as resistance to FLINAK or resistance to FLIBE melts fluorine
The application of salt material, it is characterized in that：Described compound phase is SiC, ZrB2, in TiC, Ni, Mo, Nb, W, Cu, C, Ti, Hf, Ta
One or more kinds of combinations.
5. Ti as claimed in claim 33SiC2Base ceramic material melts villiaumite as resistance to FLINAK or resistance to FLIBE melts fluorine
The application of salt material, it is characterized in that：The content of described compound phase in the base is 0.01~90wt%.
6. the Ti as described in any claim in claim 1 to 53SiC2Base ceramic material melts villiaumite as resistance to FLINAK
Or resistance to FLIBE melts the application of villiaumite material, it is characterized in that：Described Ti3SiC2Base ceramics use sintered powder technique system
It is standby.
7. Ti as claimed in claim 63SiC2Base ceramic material melts villiaumite as resistance to FLINAK or resistance to FLIBE melts fluorine
The application of salt material, it is characterized in that：Described Ti3SiC2Base ceramics using resistance heating sintering, microwave sintering, hot pressed sintering or
It is prepared by plasma discharging Fast Sintering technology.
8. the Ti as described in any claim in claim 1 to 53SiC2Base ceramic material melts villiaumite as resistance to FLINAK
Or resistance to FLIBE melts the application of villiaumite material, it is characterized in that：Described resistance to FLINAK melting villiaumites or resistance to FLIBE meltings
Villiaumite material is fusedsalt reactor structural material, the spentnuclear fuel dry method post processing functional electrode material by electrolyte of villiaumite
Material, and the alloy surface film of resistance to fluoride salt corrosion or coating material.
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| CN106083104A (en) * | 2016-06-30 | 2016-11-09 | 万燕杰 | A kind of small-sized preheating in rotary kiln device dedicated pouring material |
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| CN105985124A (en) * | 2016-06-30 | 2016-10-05 | 万燕杰 | Special castable for large-scale cement kiln flashboards |
| CN106083099A (en) * | 2016-06-30 | 2016-11-09 | 万燕杰 | A kind of rotary medium kiln preheater dedicated pouring material |
| CN106045539A (en) * | 2016-06-30 | 2016-10-26 | 张婷 | Castable for rotary kiln grate cooler wall |
| CN105967708A (en) * | 2016-06-30 | 2016-09-28 | 万燕杰 | Special castable for preheaters of rotary kilns |
| CN106045537A (en) * | 2016-06-30 | 2016-10-26 | 万燕杰 | Special castable for large-size rotary kiln preheaters |
| CN105985123A (en) * | 2016-06-30 | 2016-10-05 | 万燕杰 | Special castable for flashboards |
| CN106083101A (en) * | 2016-06-30 | 2016-11-09 | 万燕杰 | A kind of alkaline-resisting dedicated pouring material |
| CN105948773A (en) * | 2016-06-30 | 2016-09-21 | 张婷 | Casting material for calcining kiln |
| CN106116605A (en) * | 2016-06-30 | 2016-11-16 | 张婷 | A kind of cement kiln castable |
| CN107130242B (en) * | 2017-05-19 | 2019-03-26 | 中国科学院上海应用物理研究所 | The surface treatment method of the based high-temperature alloy containing ferrochrome and the part of based high-temperature alloy containing ferrochrome |
| SI3639279T1 (en) * | 2017-06-16 | 2021-12-31 | Seaborg Aps | Molten salt reactor |
| KR20210121123A (en) | 2019-01-31 | 2021-10-07 | 시보그 에이피에스 | Structural materials for molten salt reactors |
| CN112331371B (en) * | 2020-11-02 | 2021-11-09 | 西安交通大学 | Nuclear reactor plate type fuel stream melting and transferring behavior experimental device and method |
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